CN110402306A - The preparation method of acrylic fiber - Google Patents
The preparation method of acrylic fiber Download PDFInfo
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- CN110402306A CN110402306A CN201880017593.9A CN201880017593A CN110402306A CN 110402306 A CN110402306 A CN 110402306A CN 201880017593 A CN201880017593 A CN 201880017593A CN 110402306 A CN110402306 A CN 110402306A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/30—Nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
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- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- Medicinal Chemistry (AREA)
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Abstract
The present invention relates to a kind of preparation method of acrylic fiber, which includes: to provide the polymer solution comprising the acrylonitrile copolymer containing carboxylic acid group；The polymer solution of 100 parts by weight is mixed with the hydrophiling solution comprising organic solvent and ammonium hydroxide that weight ratio is 95:5 to 60:40 of 1 parts by weight to 6 parts by weight to prepare spinning solution；And by spinning solution spinning, wherein the preparation method can control the viscosity of spinning solution to improve the draftability and intensity of acrylic fiber, and can inhibit the generation of gelling.
Description
Technical field
Cross reference to related applications
This application claims in the South Korea patent application No.10- submitted in Korean Intellectual Property Office on the 29th of September in 2017
The equity of 2017-0127618, the disclosure of the application are fully incorporated in this specification by reference.
Technical field
The present invention relates to a kind of methods using the spinning solution preparation acrylic fiber for carrying out hydrophilicity-imparting treatment.
Background technique
Carbon fiber is the fibrous carbon material of the carbon amounts with 90 weight % or more, and refers to by making by polyacrylonitrile
(PAN), as the fibrous precursor of the pitch or artificial silk of petroleum-type or coal class hydrocarbon residue preparation, heat is divided in an inert atmosphere
Fiber obtained from solution.
Carbon fiber is a kind of as carbon material present in component, and there is structure and texturizing properties also to have fibre morphology
Material, and carbon material has excellent characteristic such as heat resistance, chemical stability, electric heating conductibility, is led due to low thermal expansion
The dimensional stability of cause, low-density, friction and wear characteristic, X-ray transparent, electromagnetic wave shielding performance, biocompatibility and flexible
Property, but also extraordinary characterization of adsorption can be assigned according to activation condition.
Meanwhile acrylonitrile copolymer is being widely used as the raw material of carbon fiber precursor.In general, vinyl cyanide is copolymerized
Object, which is dissolved in organic solvent or inorganic solvent, prepares spinning solution, is then spun by wet spinning, dry spinning or wet-dry process
Silk is prepared into fibre morphology, then can obtain acrylic fiber by condensation, washing, stretching and drying.
In order to be prepared in fire resistance fibre using acrylonitrile copolymer, by accelerating the flame retardant treatment of precursor fiber come really
Stability is protected, is widely used by making the monomer containing carboxylic acid group on a small quantity and copolymerization of acrylonitrile and prepares acrylonitrile copolymer
Method.In the wet process or wet-dry process spinning of the spinning solution prepared using the acrylonitrile copolymer thus prepared, in order to
It improves the hydrophily of spinning solution and inhibits small or big gap, proposing a kind of makes above-mentioned carboxylic acid group's ion using ammonium hydroxide
The method of change.However, in order to which the ammonium hydroxide for ionizing carboxylic acid group and being introduced into is easy to generate gelatin polymer in spinning solution, and
And this gelatin polymer serves as foreign matter in the spinning solution spinning process containing acrylic fiber, so as to deteriorate life
Produce stability and operability.
[existing technical literature]
[patent document]
(patent document 1) KR1999-0035887A
Summary of the invention
Technical problem
One aspect of the present invention provides a kind of acrylic fiber that can improve productivity, stability and operability
Preparation method.
Technical solution
According to an aspect of the present invention, a kind of preparation method of acrylic fiber is provided, which includes: to mention
For the polymer solution comprising the acrylonitrile copolymer containing carboxylic acid group；By the polymer solution of 100 parts by weight and 1 parts by weight
The hydrophiling solution comprising organic solvent and ammonium hydroxide that weight ratio is 95:5 to 60:40 to 6 parts by weight is mixed to prepare spinning
Stoste；And by spinning solution spinning.
Beneficial effect
The preparation method of acrylic fiber according to the present invention can during acrylonitrile copolymer hydrophiling
Ammonium hydroxide is used under specified conditions, to inhibit the generation of gelatin polymer by hydrophilicity-imparting treatment, is controlled viscosity, is thus improved and spin
The draftability and intensity of silk fiber, and be easy to carry out spinning, so as to improve the productivity of acrylic fiber, stability and
Operability.
Detailed description of the invention
Fig. 1 is the photo for showing the circularity and transparency of the acrylic fiber in embodiment 4；
Fig. 2 is the photo for showing the circularity and transparency of the acrylic fiber in comparative example 3.
Specific embodiment
Hereinafter, the present invention will be described in further detail to be more clearly understood that the present invention.
It will be appreciated that the word or term that use in the specification and claims should not be construed as in commonly used word
Meaning defined in allusion quotation.It will further be understood that the meaning of word or term can should suitably be defined based on inventor with most
Illustrate principle of the invention well, these words or term are interpreted as having and they are in the background of the relevant technologies and at these
The consistent meaning of meaning in the technical idea of invention.
The acrylic fiber of an embodiment according to the present invention may include providing comprising third containing carboxylic acid group
The step 1 of the polymer solution of alkene nitrile copolymer.
In order to promote and stablize anti-flammability, based in the monomer for preparing 100 parts by weight used in acrylonitrile copolymer,
Acrylonitrile copolymer can be by making the acrylonitrile monomer and 0.1 parts by weight to 10 weight of 90 parts by weight to 99.9 parts by weight
The carboxylic acid type monomer of part polymerize to prepare.
Carboxylic acid type monomer is not particularly limited, but can be in itaconic acid, acrylic acid and methacrylic acid
It is one or more, and can specifically itaconic acid.
Acrylonitrile copolymer can be prepared by further polymerizeing (methyl) acrylate monomer, be based on 100 weight
The monomer mixture of part, acrylonitrile copolymer can pass through (methyl) acrylate list that 0.1 parts by weight to 6 parts by weight are added
Body polymerize.(methyl) acrylate monomer is not particularly limited, but can be selected from methyl acrylate, acrylic acid second
One of ester, propyl acrylate, methyl methacrylate, ethyl methacrylate and propyl methacrylate are a variety of, and
And it specifically can be methyl acrylate.
As the polymerization of acrylonitrile copolymer, such as polymerisation in solution, suspension polymerisation and emulsion polymerization can be used
Known polymerization methods, it is contemplated that technique is convenient, preferably polymerisation in solution.The example of the solvent used in polymerisation in solution includes two
Methyl sulfoxide, dimethylformamide, dimethyl acetamide etc..In view of productivity, i.e. rate of setting, solvent can be dimethyl
Sulfoxide.
The acrylonitrile copolymer that it is 97% or more using polymerisation conversion that acrylonitrile copolymer, which can be,.Institute as follows
It states, although polymerisation conversion cannot be increased substantially since the viscosity of spinning solution has finite value in the past, works as and apply
It, can also be with even if polymerisation conversion is increased to 97% or more when the preparation method according to the present invention such as hydrophilicity-imparting treatment
Spinning is successfully carried out, therefore the carbon fiber of high quality can be provided.
The solvent for including in a polymer solution is not particularly limited, but it is preferable to use can be used for the molten of polymerisation in solution
Agent.
The pH of polymer solution can be 4 to 8, and specifically 5 to 7.Include in the polymer solution under above-mentioned pH
The content of carboxylic acid group in acrylonitrile copolymer can be derived.
Further, since polymer solution is to be prepared by polymerisation in solution, therefore polymerize the state completed and can be copolymerization
Object includes state in organic solvent.In this case, the concentration of copolymer preferably can be 15 in a polymer solution
Weight % to 25 weight %, more preferable 18 weight % to 22 weight %.That is, polymerization can be in copolymer by organic solvent diluting
It is completed under state.
The preparation method of the acrylic fiber of an embodiment according to the present invention may include by 100 parts by weight
The hydrophiling comprising organic solvent and ammonium hydroxide that weight ratio is 95:5 to 60:40 of polymer solution and 1 parts by weight to 6 parts by weight
Solution mixes to prepare the step 2 of spinning solution.
Ammonia (NH in ammonium hydroxide3) by making the carboxylic acid group for including in acrylonitrile copolymer ionization for improving hydrophily.
For the ammonia (NH in the ammonium hydroxide of hydrophilicity-imparting treatment3) it with the equivalent proportion of carboxylic acid group preferably can be 2:1 to 1.5:1, in particular
1.3:1 to 0.9:1.When meeting the above range, have the advantages that spinning solution can be inhibited to be gelled and improve hydrophilic.
This hydrophiling can be improved the circularity and the degree of packing of spinning fibre, and the intensity of the carbon fiber finally prepared and
Draftability can be improved because of these effects.
More specifically, when acrylonitrile copolymer does not carry out hydrophilicity-imparting treatment, solvent in polymer, i.e., poly-
In the water that solvent used in conjunction is diffused into polymer outer during the water condensation of spinning.In addition, (spinning is fine for polymer
Dimension) outer surface be hydrophobic, therefore the water in condensation process irregularly approach and penetrate into spinning fibre.Therefore, make
Cross section for the spinning fibre of acrylonitrile copolymer may cannot keep its original-shape, this may negatively affect carbon fiber
The quality of dimension.
However, the functional group of spinning fibre external hydrophilic or ion inhibit in hydrophilicity-imparting treatment according to the present invention
The sovent diffusion of polymeric inner is to outside, therefore the available holding of circularity of spinning fibre.
On the other hand, the water for including in the ammonium hydroxide of hydrophilicity-imparting treatment reacts that form gel poly- with acrylonitrile copolymer
Object is closed, serves as foreign matter in the spinning process that the gelatin polymer of formation can be described below, so as to deteriorate vinyl cyanide fibre
The preparation stability and operability of dimension.
When using water-free ammonia to solve this problem, in order to make ammonia in the undissolved ammonia state in ammonium hydroxide
Lower contact polymer solution, ammonia are introduced into polymer solution with an individual device, so that technique becomes complicated, and
Facility can be can increase, to improve total process costs, operating cost etc., and then had to the price competitiveness of final carbon fiber
Detrimental effects.
Therefore, because may directly be thrown into question in all fields using ammonia, therefore it is preferable to use ammonium hydroxide.In ammonium hydroxide
Water preferably comprises a small amount of so that the carboxylic acid group of acrylonitrile copolymer can contact and react with ammonia in polymer solution.
As described above, in order to eliminate do not use ammonia and the problem of using being caused when ammonium hydroxide due to water, organic solvent and ammonia
The weight ratio of water preferably can be 95:5 to 60:40, more preferably 93:7 to 70:30.When meeting the above range, having can be with
Prevent the water in ammonium hydroxide from causing the advantages of being gelled and can be improved spinning operability.
It in other words, can be by being obtained with organic solvent diluting ammonium hydroxide when polymer solution carries out hydrophilicity-imparting treatment
Said effect.When ammonium hydroxide is added directly into the polymer solution that concentration is about 15 weight % to 25 weight % without dilute
When, as noted previously, as the formation of gelatin polymer, preparation stability and operability are very high a possibility that decline.Therefore, i.e.,
Make comprising organic solvent, to be also required to the organic solvent diluting ammonia with allowance during adding ammonium hydroxide in a polymer solution
Water.In this case, thinner ratio preferably can be 95:5 to 60:40, and more preferably 93:7 to 70:30.
On the other hand, the polymer solution based on 100 parts by weight is added to the amount of the hydrophiling solution in polymer solution
It can be 1 parts by weight to 6 parts by weight, and can be controlled according to the ratio between organic solvent and ammonium hydroxide to a certain range.However,
In addition to this considers, above-mentioned amount ranges are preferably satisfied to prevent gelatin polymer from being formed.When the content of hydrophiling solution is less than 1
When parts by weight, viscosity may be excessively high；When content is greater than 6 parts by weight, viscosity may be too low.It is therefore preferable that meeting the above range.
Organic solvent is not particularly limited, it is preferred that using that can include solvent in a polymer solution.
As described above, it is total to can solve vinyl cyanide by suitably controlling the weight ratio between ammonium hydroxide and organic solvent
The all problems during gas or aqueous solution are introduced when the processing of ammonia required for polymers hydrophiling.
On the other hand, need to suitably control the viscosity of spinning solution, to prevent the outlet clogging of device for spinning
With the even compact of entire fiber etc..In general, having been carried out to control the viscosity of spinning solution and individually adding solvent
Technique, or when preparing acrylonitrile copolymer by reduction polymerisation conversion come the technique that adjusts the viscosity of polymer solution
Deng.
But such as preparing acrylonitrile copolymer by improving polymerisation conversion and being introduced separately into solvent reduces viscosity
Processing be not method appropriate for the operation of entire technique.Therefore, general using the method for reducing polymerisation conversion.
But in the case where carrying out hydrophilicity-imparting treatment according to the present invention, the effect of hydrophilicity-imparting treatment can be obtained simultaneously
With the effect of dilute polymer solution, so as to greatly improve the polymerisation conversion of acrylonitrile copolymer, therefore can make
The standby copolymer with macromolecule.As a result, can provide one kind has the advantages that improve carbon fiber physical property, and also have
There are controlled viscosities not cause the spinning solution of problem during the spinning process.
As described above, the final viscosity of the spinning solution with controlled viscosities can be 1 more than and less than 2, in particular
1.3 to 1.7.The final viscosity of spinning solution can by control polymer solution and hydrophiling solution between mixing ratio come
It arrives.When meeting the above range, in the spinning process that spinning can be described below the case where not blocking spinning head outlet
It is lower to be easy to carry out, so as to improve the productivity, stability and operability of acrylic fiber.
Final viscosity is to calculate the value that the final viscosity [η] of PAN solution obtains by application following formula 1, this is the side Huggins
The expansion relation of journey expresses formula, when [η] of HOMO-PAN is reference, calculate the relational expression fitting parameter (KH, Bn and
n)。
[formula 1]
ηsp-[η]-c
Wherein, ηsp=c [η]+KH([η])^2+Bn(c [η]) ^n ,-KH=0.367 ,-Bn=0.0156.
In addition, having [η] of minimum overall error can be by using ηsp、KH、BnWith by four kinds of concentration (0.5 weights in total
Measure the n calculating that the viscosity measurement of the PAN solution of % to 5 weight %) calculates.
In addition, the spinning solution with controlled viscosities can have in 400P to the viscosity between 650P, and can lead to
It crosses hydrophilicity-imparting treatment and obtains the viscosity.There are the feelings of the viscosity in above range in the spinning solution for preventing gelatin polymer from being formed
Under condition, productivity can be improved in spinning technique, and can continuously and steadily carry out spinning technique.
Here, viscosity be by using the viscosity of the Brookfield viscosity meter with cone rotor (CPA-52Z),
It is the shear rate and temperature point by that will measure with 3 ° of cone angle, the bevel radius of 1.2cm and 13 gaps below
The viscosity for not being set as 10-20/sec and -45 DEG C and measuring.
The pH value of spinning solution can be 9 to 11, and specifically 10 to 11, and preferably 10.4 or more.Above-mentioned pH can be with
Indicate that the hydrophily of acrylonitrile copolymer for including in spinning solution is improved, and pH can be with according to hydrophiling degree
It is higher.
The preparation method of acrylic fiber according to embodiments of the present invention may include by the step of spinning solution spinning
Rapid 3.
Spinning can be carried out with wet process, dry method or wet-dry change, especially wet process or wet-dry change.In addition, spinning can be specific
Ground is carried out to include condensation technique, a cycle of washing process and drawing process more than once.More specifically, due to condensation
The number of technique, washing process and drawing process has an impact to the structure of acrylic fiber, tensile property and compactness, therefore
Executing their total degree can suitably be adjusted, and can be 3 to 20 times.
Spinning can be carried out by using spinning head.The shape of outlet, diameter and quantity are adjustable in spinning head, with
Carbon fiber is adapted to as final products.The material for constituting spinning head is not particularly limited, but the example includes stainless steel, gold
And platinum.
Spinning solution can be discharged by spinning head from the inside of coagulation solution, then be condensed in condensation technique to prepare
Condense yarn.In addition, spinning solution can be discharged by spinning head, move a certain distance in air, then in coagulation solution
Middle condensation is to prepare condensation yarn.
The discharge rate and the velocity of discharge of spinning solution can be adjusted according to the concentration of spinning solution.
Specifically, when the diameter of outlet in spinning head is 0.07mm, and the quantity of outlet is 100, it is contemplated that stablize
Property, discharge rate can be 1cc/min to 10cc/min, and the velocity of discharge can be 0.3m/min to 4m/min, in particular 0.5m/
Min to 2m/min.Specifically, when the solvent for including in spinning solution is dimethyl sulfoxide, temperature when discharge can be 40
DEG C to 60 DEG C.When meeting above-mentioned temperature range, the mobility and final viscosity of spinning solution can be suitably kept.Work as temperature
When lower than above range, the mobility of spinning solution is deteriorated, and the final viscosity of spinning solution improves, prevent spinning is from suitable
It carries out sharply.In addition, when temperature when evacuated is lower than 19 DEG C, dimethyl sulfoxide solidification possibly can not be discharged.When more than above-mentioned
When temperature, spinning solution may change colour.
The temperature of coagulation solution can be considered coagulation solution set point and boiling point, acrylic fiber consistency and
The balance of the intensity of carbon fiber as final products determines.Specifically, the temperature of coagulation solution can be 40-60 DEG C.More
Specifically, the temperature of coagulation solution can be identical as the temperature of spinning solution.This is because only when the temperature in entire technique
It keeps constant or makes temperature and viscosity gradient to minimize when spinning solution becomes fiber with viscosity, can just prepare high-quality
Acrylic fiber.When coagulation solution temperature is lower than spinning solution temperature, the solvent between yarn and coagulation solution is condensed
Diffusion rate slows down, this facilitates the compact structure for making to condense yarn.However, mobility may decline, fiber may be not easy
Change, spinning head may be blocked in discharge process.When temperature is more than 60 DEG C, the solvent between yarn and coagulation solution is condensed
Diffusion carries out it is very fast, therefore condensation yarn compact structureization possibly can not suitably carry out.When compact structureization cannot fit
When carrying out, condense on the surface of yarn or it is internal form many holes, acrylic fiber, i.e., final products of the invention
Density may decline.
Coagulation solution is not particularly limited, as long as the spinning solution condensation of discharge can be made.Coagulation solution can
To be the mixed solution of water and organic solvent.The reason is that water can be such that acrylonitrile copolymer solidifies or vinyl cyanide can be made to be total to
Polymers forms fibers form, and organic solvent can dissolve acrylonitrile copolymer.When coagulation solution is made of 100% water
When, acrylonitrile copolymer solidifies once passing through spinning head, therefore not can be carried out fibrosis, and may also block spinning head
Outlet.Therefore, when water and organic solvent and above-mentioned coagulation solution properly mix, it can offset and be lacked by what water meter revealed
Point.
Washing can be carried out for removing remaining impurity, reagent or decentralized medium in condensation yarn.
Condensation yarn after washing can be stretched is to promote acrylic fiber fine and close, to form drawing.Relatively
1.5 times to 10 times, especially 2 can be improved times to 6 times in the whole length of condensation yarn after washing, stretching ratio.
Roller can be used and carry out drawing process.In addition, drawing process can carry out once or twice or more time, and excellent
Choosing carries out two or more times to improve carbon fiber as the intensity of final products.When carrying out stretching two or more times,
It is preferred that the difference between draft temperature is 10 DEG C to 20 DEG C.
Drawing process can 60 DEG C to 100 DEG C, especially 70 DEG C to 100 DEG C, at more specifically 80 DEG C to 100 DEG C into
Row.
It can be led to by acrylic fiber prepared by the preparation method of acrylic fiber according to embodiments of the present invention
Carry out flame retardant treatment is crossed to be formed by carbon fiber precursor.
In the present invention, it is fire-retardant can have with term " fire resisting " essentially identical meaning, and can be used including " resistance
The meaning of combustion processing ".Specifically, fire-retardant to refer to the generic term for being difficult to sustained combustion, that is, it is difficult to burn.
Furthermore, in the present invention it is possible to carry out fire-retardant so that it not only assigns acrylic fiber flame retardant property, but also
With the acrylic fiber for carrying out flame retardant treatment, i.e. the carbon fiber precursor performance that is easy to control carburizing reagent.
On the other hand, fire-retardant to be carried out while application some tension by heat treatment in oxidation or air atmosphere, and
It can carry out to convert ladder polymer for the acrylonitrile copolymer in acrylic fiber by cyclization, and lead to
Acrylonitrile copolymer is converted the polymer with aromatic rings by peroxidating and dehydrogenation reaction.
Since flame retardant treatment eliminates low molecular weight substance, and change significantly in the ingredient for constituting acrylic fiber
The chemical structure of acrylic fiber is become.
During carrying out flame retardant treatment, acrylic fiber is through yellow and the final blackening of brown.When at fire-retardant heat
When the residence time in reason area is too long, acrylic fiber may burn because of peroxidating.In addition, due in flame retardant treatment process
The exothermic reaction as caused by cyclization, oxidation reaction and dehydrogenation reaction occurred carries out suddenly in a short time, therefore, it is difficult to
Control reaction, and such exothermic reaction can destroy the chain of acrylic fiber, therefore can deteriorate the physics of carbon fiber
Performance.
Therefore, fire-retardant can be in the method for preparing carbon fiber precursor a key factor is controlled.
While applying some tension in oxidation or air atmosphere, flame retardant treatment can be carried out at 200-350 DEG C.Tool
Body, in flame retardant treatment process, it is contemplated that productivity is 10 DEG C to 20 DEG C low in the temperature than making yarn breakage due to reaction heat
At a temperature of carry out reaction be appropriate.
The specific gravity for carrying out the carbon fiber precursor of flame retardant treatment can be 1.2 to 1.5, and specifically 1.3 to 1.4.
Carbon fiber precursor can be formed by carbon fibre carbonizing.
When being carbonized, the hetero atom of such as N in carbon fiber precursor can remove, so that preparation has 90% or more
Carbon amounts and there is carbon fiber with structure as graphite-phase.
Carbonization can be the technique for heating fire resistance fibre at 1000 DEG C to 3000 DEG C in an inert atmosphere.Carbonization can root
Temperature is controlled according to the characteristic of carbon fiber to be obtained.There is high-intensitive carbon fiber in order to obtain, it can be at 2000 DEG C extremely
It is carbonized at 3000 DEG C.
Carbon fiber and can contain nitrogen as the second component containing 92% to 98% carbon amounts.Carbon fiber can be with
Containing 0.05% moisture below, stablize and do not influenced by moisture, and shows more higher than glass fibre or aramid fiber
Water resistance.In addition, carbon fiber can have excellent chemical resistance, and can have 3500MPa or more tensile strength and
The tensile modulus of elasticity of 230GPa or more.
Carbon fiber may be used as the material of aviation, sports goods, building and civil engineering.
Embodiment
Hereinafter, it will be described in the embodiment of the present invention so that those skilled in the art can be easy to carry out this hair
It is bright.However, the present invention can be embodied with many different forms, and it should not be construed as limited by embodiment listed here.
Prepare embodiment 1: the preparation of acrylonitrile copolymer
The acrylonitrile comprising 92 parts by weight, 6 parts by weight will be added to as the azodiisobutyronitrile of initiator (AIBN)
Methyl acrylate and the itaconic acid of 2 parts by weight are used to form in the composition of acrylonitrile copolymer, then in 70 DEG C of temperature
Degree is lower to carry out polymerisation in solution 14 hours, and terminating polymerization in polymerisation conversion appropriate to prepare includes acrylonitrile copolymer
Polymer solution.In this case, the concentration of polymer solution is about 21 weight %.
Embodiment 1 to embodiment 4 and comparative example 1 are to comparative example 4
Ammonium hydroxide and dimethyl sulfoxide (DMSO) are mixed to prepare hydrophiling solution, relatively with ratio shown in following table 1
The carboxylic acid (COOH) of the acrylonitrile copolymer in polymer solution prepared in preparation embodiment 1, ammonium hydroxide contain as following
Ammonia (the NH of equivalent proportion shown in table 13)。
Polymer solution and hydrophiling solution are mixed with ratio shown in following table 1 to prepare embodiment 1 to embodiment 4
With comparative example 1 to the spinning solution of comparative example 4.
[table 1]
The performance evaluation of 1. spinning solution of experimental example
According to the spinning solution that following condition evaluating embodiment 1 to embodiment 4 and comparative example 1 are prepared into comparative example 4,
As a result as shown in Table 2 below.
Measuring condition
1)The viscosity of spinning solution: viscosity is by using the Brookfield viscosimeter with cone rotor (CPA-52Z)
Measurement, the viscosimeter is with 3 ° of cone angle, the bevel radius of 1.2cm and 13 gaps below, and the shearing by that will measure is fast
Rate and temperature are respectively provided to 10/sec to 20/sec with -45 DEG C to measure.
2)The pH of spinning solution: pH sensor is inserted directly into polymer solution, stablizes 15 minutes, then measures spinning
The pH of stoste.
3)The determination of gelling: while stirring the polymer solution of 100ml at 60 DEG C, ammonia-organic solvent is added dropwise
Mixed solution so that polymer solution and ammonia-mixed solution reaction.The mixed solution of PAN is stirred 1 hour, and 12
Observation solution surface is after hour to determine gelling.
[table 2]
It referring to table 2, adjusts by the weight ratio of organic solvent and ammonium hydroxide to 95:5 to 60:40, and in 1 parts by weight to 6
In the case where the embodiment 1 to embodiment 4 for applying hydrophiling solution in the range of parts by weight, required levels of viscosity can be determined
It can be between 450P and 650P.
Specifically, from embodiment 4 and comparative example 2 it was determined that although the amount of hydrophiling solution without very big difference,
It is that viscosity differences between the two are very big.It is inferred that spinning apparatus can have by unfavorable shadow when viscosity is more than 650P
Loud higher possibility, and the draftability of fiber may deteriorate.In addition, by comparative example 1 it was determined that passing through excessive addition
The hydrophiling solution of the state for not adjusting the ratio between organic solvent and ammonium hydroxide substantially reduce viscosity.Therefore, it can push away
Disconnected, the physical property of spinning fiber, especially intensity can deteriorate.
In addition, in the case where not adding ammonium hydroxide and only add comparative example 3 of organic solvent, can determine due to pH value compared with
It is low basic without carrying out hydrophilicity-imparting treatment.Therefore, it can be seen that the very low intensity for making fiber of viscosity is adversely affected.This
Outside, in the case where only adding comparative example 4 of ammonium hydroxide, it may infer that hydrophilicity-imparting treatment is carried out according to pH.However, it is possible to predict to glue
Degree will be excessively increased, to negatively affect the draftability of device for spinning and fiber.
In addition, can determine undiluted ammonium hydroxide or diluter than adjusting not with specific in the case where comparative example 2 and comparative example 4
Concentration is released, high viscosity and gelatine are caused.I.e., it is possible to infer, when ammonium hydroxide, which does not dilute, to be just added, the draftability of spinning fibre
It may be adversely affected since viscosity increases with gelation with transparency.
The performance evaluation of acrylic fiber after 2. spinning of experimental example
(outlet diameter: 100 μm, outlet quantity: 100) water and dimethyl sulfoxide are discharged to by using spinning head
In coagulation bath containing keeping the spinning of embodiment 4 and comparative example 3 former in the coagulation solution (temperature: 50 DEG C) that weight ratio is 45:55
Liquid is condensed to prepare condensation yarn.On the other hand, spinning head is located in coagulation solution.Condensation yarn is moved to by roller from coagulation bath
In washing bath, containing water (60 DEG C) washing bath in wash, and at 95 DEG C using roller stretching to prepare acrylonitrile type fiber.
The circularity of the acrylic fiber prepared in embodiment 4 and comparative example 3, transparency, close is measured under the following conditions
Degree, gap number and maximal draw ratio, as a result as shown in Figure 1, Figure 2 and shown in table 3.
<evaluation method>
1) measurement method of circularity: it is surveyed under the enlargement ratio of 2.0k with SEM instrument (FESEM, S-4800, Hitachi)
The cross section of acrylic fiber is measured, the ratio between long axis and the short axle of cross section (major axis/minor axis) is then measured.
2) transparency: visually observe acrylic fiber.
3) it density: has already passed throughThe swelling yarn samples of hot water stretch bath are using centrifugal dehydrator with 3000rpm dehydration 15
Minute, then in 105 DEG C of baking oven dry 1 hour to measure its density (Sartorius, QUINTIX224-1SKR), for
A certain amount of fibre bundle measures the weight in the weight and ethyl alcohol in air, then calculates density using following formula 1.
[formula 1]
ρ=[Wa/ (Wa-Wl)] x ρ l
Wherein, ρ is density, and ρ l is fluid density, and Wa is the weight in air, and Wl is the weight in liquid.
4) quantity in hole: based on the density for having already passed through the swelling yarn after hot water stretch bath, relatively porosity.
5) maximal draw ratio: after fiber stretches, roller speed when being discharged into outside device for spinning by measuring fiber and
Roller speed of the roller between coagulation bath and water-bath, is calculated according to the following equation maximal draw ratio.
(maximum elongation rate)=(roller speed when being discharged into after stretching outside device for spinning)/(between coagulation bath and water-bath
Roller speed)
6)Intensity, elasticity modulus, elongation and fineness:
According to the measurement standard ISO 11566:1996 of staple fiber physical property, FAVIMAT device measuring fiber is used
Intensity, elasticity modulus, elongation and fineness.1cN/tex pre-stretching and 2.0mm/min test speed under measurement intensity,
Elasticity modulus and elongation measure fineness under the pre-stretching of 1cN/tex and the test speed of 0.5mm/min.
7) it is orientated: use powder x-ray diffraction (D4 enveador XRD 1,2,3) measurement orientation.
[table 3]
[table 4]
Referring to table 3, it can be seen that the acrylic fiber of embodiment according to the present invention 4 has low circularity, transparent, a small amount of
Gap, high density and excellent draftability.However, it is possible to determine that the acrylic fiber of comparative example 3 has the circularity, no of height
It is transparent, there is low-density, and draftability is bad.
In addition, can determine the shape of the cross section of fiber almost in the case where showing Fig. 1 of fiber of embodiment 4
Close to circle, and it can also with the naked eye determine that fiber is transparent.However, the case where showing Fig. 2 of fiber of comparative example 3
Under, the cross section of fiber can be with the naked eye determined close to " heart " shape, and fiber itself is very opaque.
In addition, referring to table 4, it can be seen that compared with the fiber of comparative example 3, the acrylic fiber of embodiment 4 owns
Physical property be all it is excellent, especially intensity improves about 20%.
From the above mentioned, when the hydrophiling solution of the ammonium hydroxide and organic solvent that are blended with proper proportion is added to spinning solution
When middle progress hydrophilicity-imparting treatment, it can be seen that may be implemented to improve the draftability of fiber, improve the circularity of fiber, and improve fine
Gap number and transparency inside dimension.
Claims (7)
1. a kind of preparation method of acrylic fiber, the preparation method include:
Polymer solution comprising the acrylonitrile copolymer containing carboxylic acid group is provided；
What it is by the polymer solution of 100 parts by weight and 1 parts by weight to 6 parts by weight is 95:5 to 60:40's comprising weight ratio
The hydrophiling solution of organic solvent and ammonium hydroxide is mixed to prepare spinning solution；And
By the spinning solution spinning.
2. preparation method according to claim 1, wherein the ammonia (NH in the ammonium hydroxide3) with the equivalent proportion of the carboxylic acid group
For 2:1 to 1.5:1.
3. preparation method according to claim 1, wherein the acrylonitrile copolymer in the polymer solution
Weight concentration is 15 weight % to 25 weight %.
4. preparation method according to claim 1, wherein the hydrophiling solution includes that weight ratio is 93:7 to 70:30
The organic solvent and the ammonium hydroxide.
5. preparation method according to claim 1, wherein the acrylonitrile copolymer is prepared as follows:
Based in the monomer mixture for preparing 100 parts by weight used in the acrylonitrile copolymer, make 90 parts by weight extremely
The carboxylic acid type monomer of the acrylonitrile monomer of 99.9 parts by weight and 0.1 parts by weight to 10 parts by weight polymerization.
6. preparation method according to claim 5, wherein the carboxylic acid type monomer is selected from itaconic acid, acrylic acid and first
One of base acrylic acid is a variety of.
7. a kind of preparation method of carbon fiber, the preparation method include:
Acrylic fiber is prepared according to claim 1；
Flame retardant treatment is carried out to the acrylic fiber；And
Make the acrylic fiber carbonization for carrying out flame retardant treatment.
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| KR10-2017-0127618 | 2017-09-29 | ||
| KR20170127618 | 2017-09-29 | ||
| PCT/KR2018/011440 WO2019066500A1 (en) | 2017-09-29 | 2018-09-27 | Acrylonitrile-based fiber manufacturing method |
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| US (1) | US11286580B2 (en) |
| EP (1) | EP3575454B1 (en) |
| JP (1) | JP6893998B2 (en) |
| KR (1) | KR102157184B1 (en) |
| CN (1) | CN110402306A (en) |
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| CN114606579B (en) * | 2020-12-03 | 2023-08-01 | 吉林碳谷碳纤维股份有限公司 | Ammoniation method and device for polyacrylonitrile spinning solution |
| EP4267784A1 (en) * | 2020-12-23 | 2023-11-01 | Cytec Industries, Inc. | A process for producing polyacrylonitrile-based fiber having controlled morphology |
| CN113337905A (en) * | 2021-05-10 | 2021-09-03 | 北京化工大学 | Polyacrylonitrile spinning solution and preparation method and application thereof |
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| EP3575454A1 (en) | 2019-12-04 |
| US11286580B2 (en) | 2022-03-29 |
| WO2019066500A1 (en) | 2019-04-04 |
| EP3575454A4 (en) | 2020-01-15 |
| EP3575454B1 (en) | 2022-11-02 |
| KR102157184B1 (en) | 2020-09-18 |
| JP6893998B2 (en) | 2021-06-23 |
| MX2019011430A (en) | 2019-12-05 |
| JP2020509251A (en) | 2020-03-26 |
| KR20190038397A (en) | 2019-04-08 |
| US20200190701A1 (en) | 2020-06-18 |
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